Textile material and method of dyeing the same



Patented Nov. 8, 1927.

UNITED STATES TENT OFFICE.

CLARENCE B. WHITE, OF MONTCLAIR, NEW JERSEY, ASSIGNOR, IBY MESNE ASSIGN- MENTS, T0 VIVATEX PROCESSES. mo, 01! LODI, NEW JERS Y, A CORPORATION OF NEW JERSEY.

TEXTILE MATERIAL AND METHOD OF D-YEING THE SAME.

No Drawing.

. The'present invention relates to waterproofed, preserved, and dyed textile-inaterial, in which term I include not only woven fabrics but also all other kinds, knitted and netted, and also threads, yarns, fibres, and the various associations thereof. One object of the invention is to provide dyed textile material which is also repellant to water and highly resistant or repellant to the injurious influences of atmospheric gases and moisture, whereby the color imparted to the material by the dye or coloring medium or media will be more permanent and less likely to fade.

Another ob ect.of the invent-ion is to produce a dyed textile material which will be highly resistant or repellant to fungous growth and bacterial attack, and which will be more repellant to water and less subject to shrinkage than materials dyed by the commonly used processes.

character which shall be capable of absorb-' ing or neutralizing acidic substances-or acid radicals which may develop from the molecular dissociation (under the influence of light, heat, moisture, or radiant energy) of the color compolinds or the color lakes with which the textile material is dyed; toproduce or deposit upon or within the fibres of the textile material, compounds or substances which have strong afiinity for the acidic ions that may be liberated through the action of the agencies noted above and which, once united with these acidic ions, hold them tightly and are not. readily dissociated therefrom, thereby preserving the fibres from the tendering which inevitably results when such ions are free to unite with or attack the cellulose of the fibre.

Another important object of the invention is to. widen the scope of and increase the varietyiof usable mineral dyes by making it possible to employ various metallic or earthy sulfids (as. coloring media) which have hitherto been undesirable if not entirely unusable because of their general tendency to oxidize into sulfates under normal meteorological influences such as those noted above; these sulfates dissociating under such influ- Applicatio n filed April 16, 1924. Serial No. 706,884.

ences with the liberation of acid ions which attack the fibres and tender the same in the well known manner.

A still further important object of the invention is to provide a method of producmg or depositing the protecting compound or substance, or the fungus or water repellant compound, within or upon the fibres,

prior to or simultaneously with the dyeing operation; for the purpose of avoiding the heat, light, and moisture, and will thereby be rendered faster to light and also. more resistant to fading in washing.

The objects above mentioned are achieved 1n the present invention-by the use, in or upon the fibres ofthetextile material, of suitable metallic compounds, preferably of metals ofthe rare earth group (among which may be mentioned thorium, cerium, neodymium; praseodymium, lanthanum, yttrium and erbium) and, in some cases, by the use of chromium, aluminum, magnesium, titanium, etc. These metals possess the important property of being precipitated as hydroxids when their compounds fareacted upon by alkaline sulfids. Many of these hy'droxids when formed or precipitatedupon orwithi'n the fibres of tex ile material impart marked erties, and, in addition, many of-the hydroxids have strong and definite colors. For example, chromium hydroxid is grayish green, cerium hydroxid is yellowish white, neodymium, hydroXid-has a: reddish tone praseodymium hydroxid has a green and erbium hydroxid a purple-red color. The hydroxids of these elements are all strongly basic, as are also their carbonates, and are in afhigh degree capable of neutralizing acids. While alkaline Sulfids precip-itate hydroxids of the above mentioned metals, on the other hand copper, nickel, cobalt, antimony, iron, cadwater, mildew, and bacteria-repellant propmium, and manganese are precipitated as acidic ions which react upon and hydrolyze the cellulose of the fibres upon which they may have been precipitated, thereby tendering the fibres and eventually renderlng the fabric useless. It is therefore of the highest importance to have present, in or upon the fibre, basic elements or compounds which will neutralize or destroy acidic ions as rapidly as the latter may be for-med and set free.

The presence of the insoluble rare earth compound (.usually an hydroxid) renders the'textile material repellant to water and to fungous and bacterial growth, as exlained in my colplending application Serial l lo. 639,219 filed ay 15, 1923.

Some of the sulfids referred to above (for example antimony, cadmium and copper sulfids) are when dry considerably resistant to oxidation, and especially so when they are occluded or embedded in a mass of basic material, or are protected from atmospher ic agencies by water repellant coatings or non-absorbent and repellent compounds such as the metallic soaps and hydroxids of the class alluded to, and I have found it practicable to precipitate cadmium, copper, antimony, nickel, cobalt, and iron, etc., as sulfids in the same chemical react-ion or process that produces hydroxids of the rare earth metals and hydroxids of aluminum, titanium, magnesium and chromium. In many such cases the resulting color is a blend of wholly mineral origin, .possessing the intrinsic fastness of mineral colors to light. Many of the shades thus produced are unique, and the colors may be further varied by various admixtures of tin, anti mony, or cadmium sulfids, used separately or combined together.

The destructive effect of sulfuric acid ions can also be avoided, or measurably. and substantially' diminished,'by the use of insoluble or diflicultly soluble compounds of the alkali earth metals, as calcium, strontium and barium, or the related magnesium, among which compounds .may be mentioned hydroxids, carbonates,;tannates, and insoluble organic compounds in general. Such compounds have a very strong affinity for the sulfuric acid ion, and once united there-' with are very difiicult of dissociation there- .tile material strongly re froin.; With the exception of magnesium, they have the advantage that the .compounds formedwith sulfuric acid are very insoluble, barium sulfate being one of the most insoluble compounds known.

The scope and utility of the invention are not limited'to the production and application of the so-called mineral dyes, but on the contrary the invention admits of a wide extension and application to the field of substantive and adjective dyeing in which organic coloring media are also used. This is strikingly illustrated in the field of direct dyes, and especially the so-called sulfur dyes, where the coloring medium is dissolved in and applied with a strong solution of sodium or other alkaline sulfid. If the sulfur dye be applied in an alkaline sulfid bath to a fabric already impregnated with a soluble salt of one or more of the elements and substances already noted, the sodium sulfid or other alkaline sulfid will decompose the impregnating salt, forming an insoluble hydroxid, which hydroxid will, as it is formed, be thoroughly permeated by the color medium, occluding it in a colloidal or gelatinous mass which when dry strongly protects it from light or radiant energy in general and from atmospheric agencies. The action is not-essentially different when used with certain mordant dyes, such as for instance those of the anthraquinone series (including alizarin), which in general are applied in strongly a1- kaline solution.

From the foregoing it will be seen that simultaneously with the actual dyeing, and as an integral part of that operation, I am able to produce or deposit upon or within the fibres, compounds which render the texllant to water and mildew and to bacterial attack, thereby making unnecessary, in most cases, any drastic after-treatment to effect such purposes. Such after-treatments almost invariably have an appreciable, and in some cases a very great, damaging effect upon I the colors and shades of the dyed material.

Except where there is danger of the production of acid radicals or ions through oxidation or breaking down of the color molecule (as in sulfid-dyed material, for example) it is not always necessary, in my invention, that the fibres of the textile material also contain or carry compounds of a strongly basic character. In other cases the requirements of fast color, non-tendering of the fibres, etc., are met by the presence of an insoluble compound which occludes or envelops the color lake. Many of the rare earth elements which inhibit or restrain the development of mildew or bacteria form insoluble fluorids, carbonates, phosphates, borates, benzoates, aluminates, stannates,

and other-insoluble compounds, which not 1 l only give the textile material advantageous water-, bacteriaand fungus-repellant properties but also furnish the necessary mordant for mordant dyes. These insoluble compounds are formed and precipitated by the action of alkaline fluorids, phosphates, borates, etc., and in many cases the precipitating solutions can be added directly to the dye bath, so that when textile material previously impregnated with soluble rare earth metal compounds is passed through the bath the latter compounds will be converted ininsoluble compounds simultaneously with, and as a part of, the actual dyeing operation. I

As is well known, some of the important dyestuffs are best applied in an alkaline bath, some in an acid bath, and others in a neutral bath. My present invention is applicable in all three cases.

For the purpose of more fully explain? ing my invention, its results, and mode of application, I give below, in detail, various examples; with the understanding, however, that the inventionis not limited thereto but can be carried out in other ways.

of being insolubilized as hydroxid by reaction with alkaline hydrate,'carbonate or sulfid. For the purpose of coloring the textile material the impregnating solution also contains a salt of a metal capable of being precipitated as a metallic sulfid of suitable color or tint by reaction with an alkaline sulfid. Among the salts capable of being converted into insoluble hydroxids I may mention chlorids, acetates and nitrates ot' the rare earthelements; and as examples of salts capable of being converted into insoluble sultids which also are capable of dyeing the textile material, I may mention any salt (preferably sulfur-free) of] iron, copper, nickel, cobalt, cadmium, antimony,and bismath. The following are excellent formulas for impregnating baths:

, Percent. \VateL r 50 Copper acetate 25 Rare earth metal acetate or acetates 25 Per cent.

\Vater 50 Copper acetate 16 Chromium acetate 18 Rare earth acetate or acetates 16 Both the above solutions when treated with sodium sulfid or other alkaline sulfid as a precipitant yield a mineral dye of an olive drab color, the shade being darker with a greater'amount of copper and lighter with a greater amount of chromium or rare earth, and hence a large variety of shades can be obtained by proper proportioning of these two ingredients. The alkaline sulfid treatment also precipitates upon or in the fibres of the textile material the rare earth metal in the form of insoluble hydroxid, which, being strongly basic, serves to neutralize any acid ions that may be set free by subsequent dissociation of the copper or chromium sulfid in the manner previously alluded to, thereby protecting the fibres from injury bythe tendering effect which such ions or radicals would otherwise have. The impregnation can be effected at ordinary temperatures, by immersing the textile material in the selected solution, long enough (usually momentarily) for thorough impregnation. The material can then be dried. with or without the use of heat, and treated with the selected precipitating bath, which may be a solution of sodium sulfid of, say, from 3 to 20 per cent strength, at practi-- cally any temperature up to boiling, according to the nature of the fibre; cotton, for example, permitting a high temperature, while silk requires a relatively low tem-. perature. I

Many dyes uffs are, or can be, applied in a strongly alkaline bath. Notable among these are the direct dyes known as sulfur, dyes which are soluble only in a strong solution of an alkaline sulfid; and dyes of the mordant type, and their prototypes,'the madder dyes. In using a dye of these classes, I first impregnate the textile material with any soluble salt (preferably an acetate) of a metal which can be precipitated in insoluble form by alkaline sulfids, hydrates or carbonates. For this purpose I prefer salts of the rare earths though I can use salts of othermetals, as aluminum, magnesiun' chromium and titanium. After impregnation the textile material is dried, and is then ready for the alkaline dye-bath. In the case of sulfur dyes,as the material passes into the dye bath the alkaline sulfid therein, usually sodium sulfid, reacts -with'the soluble salt with which the material has been impregnated and converts it into the insoluble hydroxid precipitates, and at'the same time carries into the apparently colloidal preltlt) cipi'tate on the fibre the color base of the dye-bath. In the case of alizarin, madder and other dyes requiring alkaline baths, I

with the metallic compound on the fibre, forming an insoluble soap which renders the fabric repellant to water. Preferably the metals selected for impregnating the fabric before dyeing are such as will also impart a degree of repellancy to mildew and other fungous growth; as for example the rare earth metals, especiallythorium, cerium, didymium and lanthanum.

In thecase of dyes which cannot be applied from an alkaline but require a neutral or an acid bath, I first impregnate the textile material with a rare earth element, notably thorium, cerium, lanthanum or didymium, in the form of a compound (as for'examplean acetate) fromwhich a compound can be precipitated which is insolu ble or but slightly soluble in dilute acids such as are used in acid dyeing, and in the subsequent dyeing of the impregnated material I include as a precipitant in the acid dye-bath a fluorid, phosphate, benzoate, salicylate, or othersuitable salt of an alkali metal or alkaline earth metal. Then as a result of the reaction between the salt or salts just named" and the rare earth salt the latter is converted into an insoluble compounda fluorid, phosphate, etc.', as the case may be, with the same effect as is roduced v in the case of dyes requiring alkalme'baths as described above.-

Cotton exhibits no basic properties, and hence cannot be dyed by means of certain acid colors which are available for animal fibres, and the .choice of dyestuifs for use with cotton is therefore much more limited than in the case of animal fibres, for example wool and silk, which latter occupies an intermediate position between cotton and wool. In general, cotton dying is confined to the following classes of dyestuffs:

1. Basic colors (salts of organic bases), the dying power of which lies wholly in the basic portion of the salt and requires an acid or an acid salt to develop the color. These dyes require a mordant. 1

2. Direct colors, the characteristic feature of which is that they dye cotton directly,

without mordanting. These colors fall into two distinct groups, which are known as direct cotton colors and sulfid colors. They are mostly alkali salts of sulfonated tetrazo' bases, formed by diazotizin ing example maybe given:

The cotton is first impregnated witha rare earth salt or salts, as for. example 7 cerium acetate. The impregnating solution may also contain, for example, a soluble ,inverse proportion to the amount or d e liquor in the dye bath. The sodium car onate can bereplaced by the same amount of soap. When the impregnated material is passed into the dyeing and precipitating bath the sodium fluorid converts the rare earth metal salt on the fibres into an insoluble fiuorid; and carries into the fibre, and into the fluorid precipitated thereon, a certain por ion of the dyestufi'. The sodium fluorid may be replaced by any other salt capable of producing alike effect, as for example sodium, potassium or ammonium phosphate, benzoate, salicylate, silicate, hydroxid (when not incompatible with the dyestufl), carbonate, cyanid, etc.

The sulfid colors can be applied only in a strongly alkaline bath, a circumstance that limits them, practically, to cotton, linen,

.jute, and other vegetable fibres. The usual solvent for the dye is a strong solution of sodium sulfid. In applying. my invention 'with this class the textile material is first impregnated with-soluble salt of one or more of the .metals heretofore mentioned for a like purpose. Preferably, but not necessarily, the salt is one of an acid which has no tendering efi'ectwhen dried, as for example an organic acid, say acetic'or lactic. The impregnated fabric, preferably dried, is passed into the sulfid dye bath, thereby converting the soluble metallic salts off the impregnated fibre into insoluble compounds, as for example hydroxids. At the same time the color medium disso ved in the bath is released by the decomposition of the sul-.

fid and appears intimately incorporated with p the amorphous fcolloidal or quasi-colloidal h droxid precipitated on and within the fi re. soluble salt into an insoluble compound can be effected before dyeing, in which case the dyeing operation may proceed exactly, as r with an unimpregnated fabric, butthe incorporation of'the dye is not likely 'to be as intimate or as uniform as when the insol- Ilo.

1 15 If desired, the. conversion of the I ubilization and the dyeing are effected simultaneously or by the same bath. The range of. composition of the dyeing and insolubilizing or recipitating bath is wide, the compositio epending largely upon'the particular dyestufi to be used In general,

the color medium constitutes from. five to fifteen per cent of the bath, with a variable .the members of the. class all contain hydi'oxyl groups while others contain both hydroxyl and carboxyl groups. It is not, however, necessary that the metallic baseexists in the textile material in the form of oxid or hydro'xid, inasmuch as the .colormedia of the class under consideration have the power of combining with oleates, tannates, silicates,

etc., to form the lake on or within the fibre. .In applying my. invention with mordant colors the textile material is, as in the case of the dyes already described, first-wimpregnated with the desired metallic salt, preferably an acetate, and is then dried or tightly squeezed between rollers to eliminate at least the major portion of the moisture. The dyed or squeezed fabric is next passed through the dye bath, which latter contains in addition to the color medium or media a chemical agent capable of precipitating and rendering insoluble the metallic salt or salts with which the material was impregnated. Among the precipitating or insolubilizing agents usable for the purpose, I may mention'hydrates and carbonates of the alkali metals, alkaline silicates, oleates, tannates, borates, oxalates, fluorids, phosphates, etc. In this way the necessary inorda'nting, that is,.the formation of the color lake, is effected, and at the same time. as in the other cases hereinbefore described. a substance is introduced into the textile material, in or upon the fibres thereof, which renders the latter i'epellant to water or mildew or both.

Developed colors include a group of colors which are developed upon the fibres by the successive application of their constituent parts, one of which is usually of an acid character. In applying my invention with a dye of this class the metallic compound which is precipitated upon or in the fibre -must be of such nature that it will not readlatter are, as a rule, very soluble in the fresh;

1y precipitated wet state, but many, ,as for instance thorium and. cerium hydroxids, are

rendered relatively insoluble by drying.

Zirconium hydroxid precipitated from a hot solution is almost insoluble in dilute acid solutions, although the hydroxid formed by cold precipitation is easily soluble in such solutions. The acids used to develop the colors in the dyeing operation are quite dilute and hence there is little or nodanger of dissolving the metallic. compound with which the textile material has been impregnated; and especially is this true when the impregnating compound is a phosphate, oxalate, or fluorid of the rare earth elements.

Developed colors fall into three general classes:

(a) Insoluble azo colors-These are formed by the addition of a. dissolved diazo compound to an alkaline solution of a phen01 or to an acid solution of an amido compound. The most striking example of this Susi-group is the well known pa-ranitranilin re (b) Developed direct coZors.-These are developed from primuline or from direct colors containing free amido compounds by passing the dyed material into a solution of an amine or a phenol.

(c) Bena'o-nitrol 00Zors.-With these the material is dyed by means of certain direct colors which are developed by passing the textile material into a solution of diazo compounds, as for instance diazotized paranitranilin. The process is similar to the developinent of the insoluble azo colors.

In dyeing operations in which the actual dyeing is conducted in an alkaline bath, the fixing or precipitating agent required for insolubilizing the water-repellantor mildewrepellant compound or compounds may be n general directlyincorporated with the dye bath and the insolubilizing operation is then carried on simultaneously with the dyeing of the textile material. When the dye-bath is of a. neutral character the insolubilizing can also be ett'ccted simultaneously with the dyeing, but for this purpose a. neutral precipitant must be used," as for example a fluorid, phosphate, oleate, silicate, etc. \Vith the exception of the developed dyes, such as the insoluble azo dyes and their related groups, nearly all cotton dyeing is effected with neutral or alkaline dye-baths. With silk and wool the case is'difi'erent, these materials being usually dyed in an acid bath, and in this case the fixing or precipitating .agent for insolubilizing the water-repellent or mildew-repellant compound must be such that the compound so. produced shall 'be relatively insoluble in the dilute acidity ot the acid dye bath. These conditions are met by the rare earth element compounds, which in general confer mildew-repellancy as well as affording a basis for building up waterrepellancy. Ty ical examples of precipi tated compoun s (of jrare earth elements) material simultaneously with the actual dyeing, for the reason that the peneration of the color medium of the dye is much more thorough, approximating in fact the thorough penetrationso characteristic of yarn or stock dyeing, and the result is therefore relatively faster to light and washing. Nevertheless,,

where the simultaneous method is not practicable on account of the incompatibility of the insolubilizing. media and the dye-bath, the fabric or other textile material 11 be I made water-repellant or mildewor bac eria resistant before dyeing and may then be dyed by any of the well known methods. It is important, however, where the dyeing is to be carried out with an acid bath, to

take precautions that the compound (deposited upon or within the fibres) by which the resistant or repellant properties are imparted to the material, shall be of such naturf?1 that it is relativey'insoluble in dilute aci s.

method is equall eflicacious in preventing the staggering 0 colors whlch is almost inevitable in former processes in whichan already dyed material or fabric is subjectedto treatment for the purpose of rendering it repellant to wateror resistant to bacterial attack.

I do not claim Herein they use of watersoluble salts or other compounds as media for protecting textile material from tender ing products resulting fromthe action of atmospheric'or other agencies on the coloring agent; nor do I' claim for such purposes the use of compounds of elements '(as for example calcium, strontium, barium, and zinc) vwlnch are capable of forming sulfi'ds 1n the wet way. Such compounds in solution react to form s lfids when the textile material is i and rendering the/same repellant to subse treated wi h alkaline sulfid, and the-sulfids so produced in the textile materlal not only .have no protective effect but may even in some cases be themselves a source damage to the material. e o

It is to be understood that. the invention is not limited to the specific details herein described but can be carried out in other we s without departure from its spirit as defined by the following claims.

1. "The methodof coloring textile material,

quent' tendering products, comprising color' Although the simultaneous method" is to be preferred, the subsequent dyeing ing the textile material with a metallic sulfid and depositing in the textile material, for neutralizing acid products resulting from the action of atmospheric or other agencies on the said metallic sulfid, an insoluble basic compound of an element incapable of forming a sulfid in the wet way.

2. The method of coloring textile material and rendering the same repellant to subsequent tendering products, comprising simultaneousl coloring the textile material with a metalhc sulfid and depositing in the textile material, for neutralizing acid products resulting from. the action of atmospheric or other agencies on the said metallic sulfid, an insoluble basic compound of an element incapable of forming a sulfid in the wet ,way.

3. The method of coloring textile material and rendering the same repellant to fungous .growth, bacterial attack, or tendering products, comprising impregnating the textile material with, a soluble compound of a metal (capable of reacting with an alkaline sulfid to form an hydroxid, and with a soluble compound or'another group capable of I reacting with an alkaline sulfid to form a sulfid which is capable of coloring the material, and thereafter treating the impregnated material to convert the first mentioned sol- I uble compound into an insoluble compound and the other soluble compound into a sulfid.

4. The method of coloring textile material with mineral colors and simultaneously rendering the same repellant to fungous growth, bacterial attack, or tendering products, com-, 1 0 prising impregnating the textile material 7 with soluble metallic salts'capable of reacting with alkaline sulfid, one producing thereby tan insoluble hydroxid and another a metallic sulfiid of suitable-color; and treatwing the impregnated material with an alkaline sulfid solution;

5'. The method of coloring textile material with minenal colors and simultaneously rendering the same repellant to fungous growth, 11o

bacterial attack, or tendering products, comprising impregnating the textile material with a rare earth metal compound and a compound of a metal of another group, and treating the impregnated material with an alkaline sulfidsolution whereby the first named compound is converted lnto an in; Soluble hydroxid and the second into a sulfid.

6. The methodof coloring textile material with mineral colors and simultaneously rendering the same repellant to fungous growth, bacterial attack,"or tendering products, comprising impregnating the textile material with salts of a rare. earth metal and a metal of another group, and treating the impregnated material with an alka-linelsulfid to precipitateon the textile material an inso uble hydroxid of the rare earth metal and acolored sulfid of the other metal. l

' 3 7 Textile material coloredwith sulfid and 1' containing a neutralizing compound of an element incapable of forming a sulfid in the wet Way.

8. Textile material colored with sulfid and containing a neutralizing hydroxid of an v element incapable of forming a sulfid in the wet way.

9. Textile material colored with metallic sulfid and containing aneutralizlng compound of an element incapable of forming a 10 sulfid in the Wet Way.

10. Textile material colored with metallic sulfid and containing an insoluble neutralizing compound of an element incapable of forming a sulfid in the wet way. 15

In testimony whereof I hereto aflix my signature.

CLARENCE B. WHITE. 

